JPH05287012A - Production of hydrogenated petroleum resin - Google Patents

Abstract

PURPOSE:To easily and efficiently hydrogenate a petroleum resin under mild conditions to obtain a hydrogenated petroleum resin of high quality. CONSTITUTION:100 pts.wt. petroleum resin is mixed with at least 10 pts.wt. at least one solvent selected from among saturated chain hydrocarbons, saturated cyclic hydrocarbons, and aromatic hydrocarbons all of which have boiling points at atmospheric pressure of substantially 140-280 deg.C. The resulting resin is hydrogenated at an elevated pressure in the presence of a hydrogenation catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a hydrogenated petroleum resin. More specifically, a petroleum resin having an aromatic and / or olefinic unsaturated bond is mixed with a limited solvent and hydrogenated under pressure in the presence of a catalyst, which is easy to handle, highly economical, and high quality hydrogenation. The present invention relates to a method for producing petroleum resin.

[0002]

BACKGROUND OF THE INVENTION Petroleum resins are spent fractions of C4 to C6 aliphatic olefins obtained by pyrolysis of petroleum naphtha or catalytic cracking using a catalyst, and aromatic carbonization of C8 or more having an olefinic unsaturated bond. C5 obtained by homopolymerization or copolymerization of one or more kinds of polymerizable substances contained in the spent fraction of hydrogen with a Friedel-Crafts type catalyst or heat.
, C9 and C5-C9 copolymerized petroleum resins, as well as terpene resins and natural rosins.

Since these petroleum resins have tackiness, adhesiveness, and compatibility with other resins, they are mixed with various plastics, rubbers, and oily substances to form paints, printing inks,
Used for applications such as adhesives, adhesives, and traffic paints.

However, petroleum resins are generally colored yellow to light brown, have a peculiar odor, have low thermal stability, and have low weather resistance.

As a solution to this problem, there is a method of hydrogenating a petroleum resin in the presence of a catalyst, and the resin obtained by this method is a hydrogenated petroleum resin. This hydrogenated petroleum resin is usually colorless and transparent to white, has no odor, has excellent heat stability and weather resistance, and has high adhesiveness and tackiness. Further, it has excellent compatibility with various plastics such as rubber, polyolefin, and ethylene-vinyl acetate copolymer. Therefore, it is widely used not only in the fields of food and sanitary but also in fields requiring high quality such as hot melt adhesives, printing applications and various plastic modifiers.

By the way, the hydrogenation reaction of petroleum resin is much more difficult than the hydrogenation reaction of its monomer, and harsh reaction conditions are required to carry out the hydrogenation. In particular, hydrogenation of C9 petroleum resin containing aromatic nuclei requires more severe conditions than that of C5 petroleum resin. For example, Japanese Examined Patent Publication No. Sho 49-32438,
Column 2, lines 2-4, C using Ni-diatomaceous earth catalyst
In the production of 9-based petroleum resin, in the presence of a catalyst concentration of 10% by weight,
It describes hydrogenation under severe conditions such as a reaction temperature of 300 ° C., a hydrogen pressure of 200 Kg / cm ² , and a reaction time of 6 hours or more. Under such conditions, deterioration of the expensive catalyst is extremely large, and the catalyst equipment becomes large-scale. or,
The decomposition of petroleum resin is also large and the quality becomes unstable.

On the other hand, there is a method of hydrogenating a petroleum resin using a saturated hydrocarbon such as cyclohexane, heptane or hexane as a diluting solvent (for example, JP-A-57-2122).
No. 02). However, even with these solvents,
Efficient and effective hydrogenation is difficult under mild conditions.

Further, in Japanese Patent Laid-Open No. 2-215802,
It has been proposed to use methylcyclohexane and / or ethylcyclohexane as the solvent. This method is certainly easier to hydrogenate than the above-mentioned solvents. However, the hydrogenation efficiency is still unsatisfactory, and there are problems that the solvent is not general and expensive.

[0009]

As described above, although the hydrogenated petroleum resin has excellent physical properties and has a wide range of fields of use due to its characteristics, its production method is not satisfactory and is harsh. Conditions are forced. SUMMARY OF THE INVENTION The present invention aims to solve the above problems in production and provide a method for economically and efficiently producing a hydrogenated petroleum resin having excellent quality.

[0010]

The inventors of the present invention can easily and efficiently achieve hydrogenation of petroleum resins even under mild conditions.
Furthermore, the inventors have earnestly studied a production method capable of obtaining a high-quality hydrogenated petroleum resin. As a result, they have found that the above object can be achieved by hydrogenating a petroleum resin under pressure using a hydrogenation catalyst in the presence of a limited solvent, and have completed the present invention.

That is, the present invention relates to a petroleum resin and a petroleum resin 1
The boiling point at atmospheric pressure is substantially 140 to 2 relative to 00 parts by weight.
Mixing 10 parts by weight or more of one or more solvents selected from saturated chain hydrocarbons, saturated cyclic hydrocarbons and aromatic hydrocarbons at 80 ° C., and hydrogenating under pressure in the presence of a hydrogenation catalyst. And a method for producing a hydrogenated petroleum resin.

The petroleum resin in the present invention is a spent fraction obtained by thermal cracking of petroleum naphtha or catalytic cracking using a catalyst, and has polymerizable styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, C9-based petroleum resin, isoprene, pentene, pentadiene, methylbutene, etc. obtained by polymerizing C9 fraction mainly containing indene, dicyclopentadiene, alkylindene, ethylbenzene, trimethylbenzene, naphthalene, etc. with a Friedel-Crafts type catalyst or heat. C as the main component
C5 petroleum resin obtained by polymerizing 5 fractions in the same manner, C5 -C9 petroleum resin obtained by copolymerizing the C5 fraction and C9 fraction, and DC obtained by polymerizing cyclopentadiene.
PD petroleum resin, DCPD-St petroleum resin obtained by copolymerizing cyclopentadiene and styrene, limonene,
Terpene-based petroleum resin obtained by polymerizing pinenes, coumarone-based petroleum resin obtained mainly by polymerizing coumarone,
Natural rosin and the like can be used.

However, in order to carry out the present invention more effectively and efficiently, C9-based petroleum resin or C5-C9-based petroleum resin is preferable, and it is easy to achieve a high hydrogenation rate under mild conditions which were difficult in the past. Can be carried out. Moreover, the quality of the hydrogenated petroleum resin obtained is high, and it can be suitably used for the many important uses mentioned above.

More preferably, the spent fraction is a C9 petroleum resin obtained by polymerizing a C9 fraction having a boiling point of 140 to 280 ° C under normal pressure, or the C9 fraction and the C9 fraction.
It is a C5-C9 petroleum resin obtained by copolymerizing 5 fractions (preferably a boiling point at normal pressure of 15 to 70 ° C). In this case, the effect and efficiency are further enhanced, and higher quality hydrogenated petroleum resin can be obtained. Here, “substantially” means that most of the components constituting the petroleum resin are in the boiling point range,
More specifically, it usually means 80% or more.

Next, the present invention is one kind selected from saturated hydrocarbons, saturated cyclic hydrocarbons and aromatic hydrocarbons having a boiling point of 140 to 280 ° C. at atmospheric pressure per 100 parts by weight of petroleum resin. It is essential to mix 10 parts by weight or more of the above solvent with the petroleum resin. This is the essence of the present invention.

As a result of many years of research on a production method capable of obtaining a higher quality hydrogenated petroleum resin under milder conditions, the present inventors have found the above-mentioned solvent and its use amount, and have been able to effectively and efficiently produce petroleum oil. It has been found that the resin can be hydrogenated, the subsequent catalyst separation and the separation with the product hydrogenated petroleum resin can be easily achieved, and a high-quality hydrogenated petroleum resin can be obtained.

Specific solvents include saturated chain hydrocarbons such as n-nonane, 2-methyl-nonane and 3-methyl-
Nonane, 4-methyl-nonane, n-decane, iso-decane, 2-methyldecane, 3-methyldecane, 4-methyldecane, n-undecane, 2-methylundecane, 3-
Methylundecane, 4-methylundecane, n-dodecane, iso-dodecane, 2-methyldodecane, 3-methyldodecane, 4-methyldodecane, 5-methyldodecane,
2,3-dimethyldodecane, 2,3,4-trimethyldodecane, 2,3,4,5-tetramethyldodecane, n-
Tridecane, methyltridecane, dimethyltridecane,
Trimethyltridecane, n-tetradecane, methyltetradecane, dimethyltetradecane, trimethyltetradecane, pentadecane, alkylpentadecane, hexadecane, alkylhexadecane, heptadecane, alkylheptadecane, octadecane, alkyloctadecane, alkyloctadecane, nonadecane, alkylnonadecane, eicosane, alkyl Eikosan, etc. can be mentioned. Examples of the saturated cyclic hydrocarbon include trimethylcyclohexane, tetramethylcyclohexane, methylethylcyclohexane, bicyclohexane, methylbicyclohexane, dimethylbicyclohexane, ethylbicyclohexane, methylethylbicyclohexane, diethylbicyclohexane and the like. Examples of aromatic hydrocarbons include diethylbenzene, trimethylbenzene, tetramethylbenzene, methylethylbenzene, isopropylbenzene, P-cymene, amylbenzene, naphthalene, alkylnaphthalene, cyclohexylbenzene, alkylcyclohexylbenzene, fluorene and alkylfluorene. .. These may be one kind or a mixture of two or more kinds.

Solvents having a boiling point under atmospheric pressure of less than 140 ° C. are not included in the present invention. A solvent having a low boiling point increases the pressure during hydrogenation, requires high-pressure operation, and makes the equipment complicated and expensive. Also, a solvent having a boiling point of more than 280 ° C. under normal pressure is not included in the present invention. Although a solvent having a high boiling point is good in pressure, the hydrogenation rate, which is the first purpose, is reduced, and the efficiency is lowered. Further, it becomes difficult to separate the product from the hydrogenated petroleum resin.

Boiling point at atmospheric pressure is substantially 140 to 280 ° C.
The present invention can be achieved for the first time by using 10 parts by weight or more of the saturated chain hydrocarbon, saturated cyclic hydrocarbon, and aromatic hydrocarbon of 100 parts by weight of the petroleum resin. That is, the hydrogen addition rate can be increased even under mild conditions, and the equipment can be simplified, the operation is easy, and the productivity can be improved. Furthermore,
Almost no decomposition of solvent and petroleum resin (including hydrogenated petroleum resin), high quality hydrogenated petroleum resin can be obtained, easy separation with catalyst afterwards, and separation of solvent and hydrogenated petroleum resin Will also be easier. Further, the solvent after separation can be reused, which is economical. Further, although the principle is not clear, one of the characteristics is that the life of the catalyst is improved.

In the present invention, the boiling point at atmospheric pressure is substantially 140
The meaning of ˜280 ° C. is that, in many cases, the solvent used is not a single compound but a mixed system. In this case, although the ratio is small, it may be out of the boiling range. Even in that case, if the ratio is small, the object of the present invention can be sufficiently achieved. In addition, during hydrogenation, although the quantity is extremely small, the petroleum resin-part molecules may be cut off to reach the boiling point range of the solvent. In that case, the substance can be used as a solvent as it is, which is economical.

The hydrogenation rate can be increased under milder conditions, the deterioration of the solvent is small, the separation with the catalyst in the post-process and the separation with the hydrogenated petroleum resin are easy, and the high-quality petroleum resin is high in quality. A preferred solvent is a saturated chain hydrocarbon because it can be easily obtained in a yield, the solvent can be easily reused, the reuse ratio is high, and the solvent is inexpensive and easily available. More preferably, it is a saturated chain hydrocarbon composed of a plurality of compounds. These can further enhance the effect. On the other hand, aromatic hydrocarbons are convenient when the hydrogenation rate may be low (partially hydrogenated petroleum resin), but when it is necessary to increase the hydrogenation rate, the solvent will also be hydrogenated and saturated. It becomes a cyclic hydrocarbon. However, in this case, if the saturated cyclic hydrocarbon produced is within the range of the present invention, it exhibits the action and effect as a solvent in the present invention, and thus may be used as it is.

In the present invention, more than 10 parts by weight of solvent is used for 100 parts by weight of petroleum resin. As a result of detailed study by the present inventors, a surprising fact has been found. That is, the viscosity of the petroleum resin and the solvent was drastically decreased and the hydrogenation rate was remarkably improved at 10 parts by weight or more shown in the present invention. Usually, these change in proportion to the mixing ratio with respect to the value alone. And, in this range, many of the above-mentioned features were developed. A preferred range is 10 to 150 parts by weight,
More preferably, it is 20 to 100 parts by weight. In the preferable range, the effect becomes larger. When the amount of solvent used increases, the production efficiency decreases, the size of the solvent separation / recovery device increases, and more energy is required.

As the hydrogenation catalyst in the present invention, any catalyst having hydrogenation ability can be used without any particular limitation. For example, a Group VIII metal, that is, a metal such as nickel, palladium, platinum, cobalt, rhodium, or ruthenium alone or Ia, IIa, Ib, IV.
Among the metals or oxides of a, those composed of one kind or a combination of two or more kinds can be used, and those carrying these on a carrier such as alumina, silica, diatomaceous earth, activated carbon, titania, etc. are used. Particularly preferably, the main component is nickel metal, and the promoter components are Mg, Ca, Ba, Sr.
Is a hydrogenation catalyst in which one or more kinds of oxides, hydroxides and carbonates selected from the alkaline earth metals are supported on a diatomaceous earth carrier (Japanese Patent Application No. 3-156053). The catalyst suppresses sintering of nickel particles due to heat, and also suppresses poisoning of the catalyst by sulfur compounds usually contained in petroleum resins. As a result, the catalyst life is extended and it can be used repeatedly,
Economic efficiency is significantly improved.

Further, it is preferable to use Cu metal as a co-catalyst instead of the alkaline earth metal because the same effect is exhibited.

The amount of hydrogenation catalyst used is not particularly limited.
This is because the specific surface area of the catalyst, the amount of metal and its degree of dispersion, the type and content of co-catalyst, the hydrogenation rate, the type of petroleum resin, the content of its sulfur compounds, the hydrogenation conditions, etc. are greatly different. However, it is usually 0.1 to 100 parts by weight of petroleum resin.
It is 30 parts by weight, and is appropriately determined.

There is no limitation on the shape of the catalyst, either powder or pellets can be used.

The hydrogenation reaction conditions should be determined according to the type of petroleum resin, the content of sulfur compounds, the type and amount of hydrogenation catalyst, or the desired properties of the hydrogenated petroleum resin. Is a reaction temperature of 150 to 320 ° C., a reaction pressure of 30 to 300 Kg / cm ² , and a reaction time of 1 to 10 hours.

After the completion of the hydrogenation reaction, the desired hydrogenated petroleum resin can be obtained by separating the catalyst, usually by filtration, and usually by distilling the solvent. At the time of separating the catalyst, the catalyst may be washed with the same solvent. Also, the recovered solvent is easy to reuse.

The form of the hydrogenation reaction is not particularly limited and can be carried out by a usual method. For example, a batch type suspension bed system, a flow type fixed bed system, a flow type suspension bubble column system and the like can be implemented.

If the obtained hydrogenated petroleum resin is granulated in the form of beads, the handleability is improved.

The hydrogenated petroleum resin obtained by the present invention is colorless and transparent and has no odor, and is excellent in heat resistance and weather resistance, and has adhesiveness.
It has high adhesiveness and is useful and effective as an adhesive, an adhesive, and an additive for rubber, paint, ink, etc.

[0032]

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.

Example 1 A commercially available stainless steel pressure vessel having an internal volume of 300 ml equipped with an electromagnetic stirrer and a heater was placed on a commercially available C9 petroleum resin (Tosoh Corporation, Petcoal 120ARK, softening point 120 ° C.,
Sulfur content 120ppm, Gardner color number 12) 70
g, Ni / diatomaceous earth catalyst as hydrogenation catalyst [manufactured by N company, Ni
(Containing 50 wt%) 0.7 g, commercially available paraffinic hydrocarbon as a solvent (manufactured by I, bp: 160 to 200 ° C.) 21
g was charged, the atmosphere was replaced with nitrogen gas and then with hydrogen gas, and then hydrogen was pressurized. Next, the mixture was stirred, heated, and kept at a temperature of 250 ° C. for 5 hours. During this time, the pressure is 100 Kg / cm ² . Maintained at G. Then, the mixture was allowed to cool, the reaction product was taken out, and the catalyst and the reaction product were separated using a pressure filter. Next, the reaction product was heated in an oil bath and the solvent was removed by passing N ₂ gas to obtain a hydrogenated petroleum resin. When the hydrogenated petroleum resin was analyzed, the hydrogenation rate was 88.1% and the hue was APHA2.
It was 0 or less and colorless and transparent. There was no odor at all. The results are shown in Table 1.

Example 2 A hydrogenated petroleum resin was obtained in the same manner as in Example 1 except that the amount of the solvent added was 70 g. The hydrogenated petroleum resin obtained had a hydrogenation rate of 89.4%, a hue of APHA 20 or less, and was colorless and transparent and odorless. The results are shown in Table 1.

Example 3 As a solvent, a commercially available paraffin hydrocarbon (manufactured by Company E, boiling point 1
A hydrogenated petroleum resin was obtained in the same manner as in Example 1 except that 50 to 175 ° C.) was used. The hydrogenated petroleum resin thus obtained had a hydrogenation rate of 85.4%, a hue of APHA 20 or less, and was colorless and transparent and odorless. The results are shown in Table 1.

Example 4-1 Ni / Mg / diatomaceous earth catalyst as a hydrogenation catalyst (Japanese Patent Application No. 3-
A hydrogenated petroleum resin was obtained in the same manner as in Example 1 except that 160553) was used. The hydrogenation rate of the obtained hydrogenated petroleum resin was as high as 91.2%, the hue was APHA 20 or less, colorless and transparent, and odorless. The results are shown in Table 1.

Example 4-2 A hydrogenated petroleum resin was obtained in the same manner as in Example 4-1, except that the catalyst used in Example 4-1 was recovered and used.
The hydrogenated petroleum resin obtained had a hydrogenation rate of 89.2% and a hue of A.
It had a PHA of 20 or less, was colorless and transparent, and was odorless. The results are shown in Table 1.
Shown in.

Example 5 A hydrogenated petroleum resin was obtained in the same manner as in Example 1 except that 2.1 g of Ni / diatomaceous earth catalyst was used as the hydrogenation catalyst. The hydrogenation rate of the obtained hydrogenated petroleum resin was as high as 98.3%, the hue was APHA 20 or less, colorless and transparent, and odorless. The results are shown in Table 1.

Example 6 A hydrogenated petroleum resin was obtained in the same manner as in Example 1 except that PetroTac 90 (manufactured by Tosoh Corporation, softening point 90 ° C., sulfur content 100 ppm) was used as the petroleum resin. The hydrogenation rate of the obtained hydrogenated petroleum resin was as high as 91.8%, and the hue was A.
It had a PHA of 20 or less, was colorless and transparent, and was odorless. The results are shown in Table 1.
Shown in.

Comparative Example. 1 Example 1 except that the reaction was carried out without using a solvent
The same procedure was followed to obtain a hydrogenated petroleum resin. The hydrogenated petroleum resin thus obtained had a hydrogenation rate of 75.5% and a hue of APHA20. The results are shown in Table 1.

Comparative Example 2-1 A hydrogenated petroleum resin was obtained in the same manner as in Comparative Example 1 except that the reaction pressure was 200 Kg / cm ² · G. The hydrogenated petroleum resin obtained had a hydrogenation rate of 86.7% and a hue of APHA.
It was 20 or less. The results are shown in Table 1.

Comparative Example 2-2 The same procedure as in Comparative Example 2-1 was carried out using the entire amount of the catalyst separated and recovered in Comparative Example 2-1 (with some hydrogenated petroleum resin attached). The hydrogenated petroleum resin thus obtained had a hydrogenation rate of 70.2% and a hue of APHA of 20 or less. The results are shown in Table 1.

Comparative Example 3 A hydrogenated petroleum resin was obtained in the same manner as in Comparative Example 1 except that the reaction temperature was 290 ° C. The hydrogenation rate of the obtained hydrogenated petroleum resin was 88.1%, and the hue was APHA 20 or less. The results are shown in Table 1. Further, the obtained hydrogenated petroleum resin was analyzed by liquid chromatography, and it was found that the hydrogenated petroleum resin was considerably decomposed during hydrogenation and had a low molecular weight.

[0044]

[Table 1]

[0045]

According to the present invention, a high-quality hydrogenated petroleum resin can be efficiently and effectively produced, that is, economically, from a petroleum resin. The effects will be listed below. (1) Hydrogenated petroleum resin can be manufactured under milder conditions, which can reduce manufacturing equipment cost, improve operability, and improve safety. (2) Even in the C9-based petroleum resin and the C5-C9-based petroleum resin, which have conventionally required severe reaction conditions, the hydrogenation reaction conditions can be made milder. (3) Deterioration of petroleum resin and hydrogenated petroleum resin at the time of hydrogenation is small, and a high hydrogenation rate can be achieved, and high quality hydrogenated petroleum resin can be produced. (4) The recovery rate of hydrogenated petroleum resin, solvent and hydrogenation catalyst is high, which is economical. (5) It is easy to recover and reuse the solvent and the hydrogenation catalyst. (6) The life of the hydrogenation catalyst is improved.

[Procedure amendment]

[Submission date] April 7, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

Example 3 As a solvent, a commercially available paraffin hydrocarbon (manufactured by Company E, boiling point 1
A hydrogenated petroleum resin was obtained in the same manner as in Example 1 except that 50 to 175 ° C.) was used. The hydrogenated petroleum resin thus obtained had a hydrogenation rate of 86.4%, a hue of APHA 20 or less, and was colorless and transparent and odorless. The results are shown in Table 1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

Comparative Example 2-1 A hydrogenated petroleum resin was obtained in the same manner as in Comparative Example 1 except that the reaction pressure was 200 Kg / cm ² · G. The hydrogenated petroleum resin obtained had a hydrogenation rate of 88.4% and a hue of APHA.
It was 20 or less. The results are shown in Table 1.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

Comparative Example 2-2 The same procedure as in Comparative Example 2-1 was carried out using the entire amount of the catalyst separated and recovered in Comparative Example 2-1 (with some hydrogenated petroleum resin attached). The hydrogenated petroleum resin thus obtained had a hydrogenation rate of 70.2% and a hue of APHA20. The results are shown in Table 1.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

Comparative Example 3 A hydrogenated petroleum resin was obtained in the same manner as in Comparative Example 1 except that the reaction temperature was 290 ° C. The hydrogenated petroleum resin thus obtained had a hydrogenation rate of 88.4% and a hue of APHA 20 or less. The results are shown in Table 1. Further, the obtained hydrogenated petroleum resin was analyzed by liquid chromatography, and it was found that the hydrogenated petroleum resin was considerably decomposed during hydrogenation and had a low molecular weight.

Claims (3)

[Claims] 1. A petroleum resin, and selected from saturated chain hydrocarbons, saturated cyclic hydrocarbons, and aromatic hydrocarbons having a boiling point of 140 to 280 ° C. at normal pressure with respect to 100 parts by weight of petroleum resin. A method for producing a hydrogenated petroleum resin, which comprises mixing 10 parts by weight or more of one or more solvents and hydrogenating under pressure in the presence of a hydrogenation catalyst. 2. A C9 petroleum resin obtained by polymerizing a C9 fraction obtained by thermal decomposition of petroleum naphtha or catalytic cracking using a catalyst with a Friedel-Crafts type catalyst, or a C9 fraction of the petroleum resin. C5 -C obtained by copolymerizing C5 fraction
The method according to claim 1, which is a 9-based petroleum resin. 3. The solvent according to claim 1, which is a saturated chain hydrocarbon.
Alternatively, the method according to claim 2.